# US 5,347,048 A · Process for producing (.+-.)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin

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- Number: US 5,347,048 A
- Document ID: US5347048A
- Status: Granted
- Kind: A
- Application number: 08/116,605
- Filed: 1993-09-07
- Granted: 1994-09-13
- Earliest claimed: 1991-12-29
- Assignees: Kuraray Co., Ltd.
- Inventors: Goro Asanuma; Yoshin Tamai
- Web page: https://patentgrep.com/patent/US5347048A

## CPC

- C07D 307/92: Naphthofurans; Hydrogenated naphthofurans
- C07B 57/00: Separation of optically-active compounds
- C07C 29/147: of carboxylic acids or derivatives thereof
- C07C 29/40: with compounds containing carbon-to-metal bonds
- C07C 35/36: the condensed ring system being a [4.4.0] system, e.g. hydrogenated naphthols
- C07C 45/62: by hydrogenation of carbon-to-carbon double or triple bonds
- C07C 51/487: by treatment giving rise to chemical modification (by chemisorption C07C51/47)
- C07C 57/26: containing rings other than six-membered aromatic rings
- C07C 59/11: containing rings
- C07C 403/08: by hydroxy groups
- C07C 403/12: by esterified hydroxy groups
- C07C 403/20: having side-chains substituted by carboxyl groups {or halides, anhydrides, or (thio)esters thereof}
- C11B 9/0076: {the hetero rings containing less than six atoms}
- C07C 2601/16: the ring being unsaturated
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C11B: PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES (drying-oils C09F)

## Abstract

A process for producing (.+-.)-2,2,2,5a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin, comprising the steps of allowing a carbonate of dihydro-.beta.-vinyl-ionol to react with carbon monoxide in the presence of a palladium catalyst to form .beta.-monocyclohomofarnesic acid, cyclizing said .beta.-monocyclohomofarnesic acid in the presence of an acid catalyst to form (.+-.)-norambreinolid, and hydrolyzing said (.+-.)-norambreinolide to form (.+-.)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin.

## Claims

### Claim 1

A process for producing (.+-.)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin, comprising the steps of:
allowing a carbonate of dihydro-.beta.-vinyl-ionol according to the following formula: ##STR6## wherein R is an alkyl group, to reach with carbon monoxide in the presence of a palladium catalyst to form .beta.-monocyclohomofarnesic acid;
cyclizing said .beta.-monocyclohomofarnesic acid in the presence of an acid catalyst to form (.+-.)-norambreinolide, according to the following reaction: ##STR7## and hydrolyzing said (.+-.)-norambreinolide to form (.+-.)-2,5,5,8a-tetramethyl-1-(carboxymethyl)-2-hydroxydecalin.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the palladium catalyst is a divalent salt of palladium.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the palladium catalyst is a catalyst comprising zero valence palladium.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the palladium catalyst is used in the amount of from 0.001 to 50% by weight based on the carbonate of dihydro-.beta.-vinyl-ionol.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the palladium catalyst is used in the amount of from 2 to 10% by weight based on the carbonate of dihydro-.beta.-vinyl-ionol.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the palladium catalyst is used in the amount of from 4 to 6% by weight, based on the carbonate of dihydro-.beta.-vinyl-ionol.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the palladium catalyst is a supported catalyst.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the supported catalyst is palladium carbon.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the palladium carbon is present in the amount of from 3- to 5-fold equivalent weight, based on metallic palladium supported on palladium carbon.

### Claim 10 (depends on 1)

The method according to claim 1, wherein said carbonate of dihydro-.beta.-vinyl-ionol reacts with carbon monoxide in the presence of a palladium catalyst and a solvent selected from methanol, ethanol, or isopropanol, to form said .beta.-monocyclohomofarnesic acid.

### Claim 11 (depends on 10)

The method according to claim 10, wherein said solvent is isopropanol.

### Claim 12 (depends on 10)

The method according to claim 10, wherein said solvent is used in the amount of from about 0.5- to 10-fold by weight based on the carbonate of dihydro-.beta.-vinyl-ionol.

### Claim 13 (depends on 10)

The method according to claim 10, wherein said solvent is used in the amount of from about 3- to 7-fold by weight based on the carbonate of dihydro-.beta.-vinyl-ionol.

### Claim 14 (depends on 1)

The method according to claim 1, further comprising introducing carbon monoxide into a reaction vessel at a gas pressure of from 40 to 60 atmospheres, and then allowing said carbonate of dihydro-.beta.-vinyl-ionol according to formula (5) to react with said carbon monoxide in the presence of a palladium catalyst at a reaction temperature of from 40.degree. to 60.degree. C. to form .beta.-monocyclohomofarnesic acid.

### Claim 15 (depends on 1)

The method according to claim 1, wherein said cyclizing of .beta.-monocyclohomofarnesic acid occurs in the presence of an acid catalyst selected from mineral acids, Lewis acids, or sulfonic acids.

### Claim 16 (depends on 15)

The method according to claim 15, wherein said acid catalyst is chlorosulfonic acid.

### Claim 17 (depends on 1)

The method according to claim 1, wherein said cyclizing of .beta.-monocyclohomofarnesic acid occurs in the presence of an acid catalyst and a solvent, said solvent selected from nitroalkanes, chlorinated hydrocarbons, ethers, or acetonitrile.

### Claim 18 (depends on 17)

The method according to claim 17, wherein said solvent is dichloromethane.